WO2013161703A1 - 成型触媒の製造方法および該成型触媒を用いるジエンまたは不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 - Google Patents
成型触媒の製造方法および該成型触媒を用いるジエンまたは不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 Download PDFInfo
- Publication number
- WO2013161703A1 WO2013161703A1 PCT/JP2013/061624 JP2013061624W WO2013161703A1 WO 2013161703 A1 WO2013161703 A1 WO 2013161703A1 JP 2013061624 W JP2013061624 W JP 2013061624W WO 2013161703 A1 WO2013161703 A1 WO 2013161703A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- producing
- molded
- reaction
- molded catalyst
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims 4
- 150000001993 dienes Chemical class 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 230000001133 acceleration Effects 0.000 claims abstract description 28
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- 238000005469 granulation Methods 0.000 claims abstract description 10
- 230000003179 granulation Effects 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims description 38
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001882 dioxygen Inorganic materials 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000203 mixture Substances 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Chemical group 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Chemical group 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Chemical group 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
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- 150000001875 compounds Chemical class 0.000 description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 9
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- 150000001299 aldehydes Chemical class 0.000 description 6
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- 239000012153 distilled water Substances 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- 229910001220 stainless steel Inorganic materials 0.000 description 3
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- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
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- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- 238000003763 carbonization Methods 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- 235000010333 potassium nitrate Nutrition 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
- B01J37/0223—Coating of particles by rotation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
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Definitions
- the present invention relates to a method for producing a molded catalyst used for the production of dienes or unsaturated aldehydes and / or unsaturated carboxylic acids.
- Unsaturated carboxylic acids such as acrylic acid and methacrylic acid used as raw materials for various chemicals can be produced by a two-step reaction using an unsaturated aldehyde as an intermediate product.
- Acrylic acid and methacrylic acid are both steadily increasing in demand, and therefore the catalyst used for production is being improved energetically.
- butadiene an important chemical raw material used as a raw material for synthetic rubber and the like, has been rapidly increasing in demand as a raw material for energy-saving automobile tires in recent years due to increasing global automobile demand and environmental awareness. Yes.
- the production amount of the C4 fraction is decreasing, the shortage of butadiene production continues, and it is expected that the shortage of butadiene supply will accelerate further in the future. For this reason, industrialization of a new butadiene production method is strongly desired.
- a method for producing an unsaturated aldehyde and / or an unsaturated carboxylic acid by a selective oxidation reaction of an unsaturated hydrocarbon in a fixed bed reactor using a composite metal oxide catalyst containing molybdenum as an essential component is well known. Further, a method for producing butadiene from n-butene in a fixed bed reactor using a composite metal oxide catalyst containing molybdenum as an essential component is also well known.
- the shape of the catalyst used in the fixed bed reactor is selected according to the application, but there are ring shape, cylinder shape, tablet shape, honeycomb shape, three-leaf type, four-leaf type, and even a spherical catalyst shape. Well used.
- spherical catalysts are widely used because of the ease of filling the reaction tube with the catalyst and removing the used catalyst from the reaction tube.
- the method of supporting and molding a catalytically active component on an inert carrier is widely used industrially for the purpose of reducing the heat storage of the catalyst layer, etc. in use. In particular, it is used as an effective method when an objective product is selectively produced by an oxidation reaction or oxidative dehydrogenation reaction of an organic compound.
- Patent Document 1 discloses a method for producing acrolein and / or acrylic acid from propylene
- Patent Document 2 discloses methacrolein and / or methacryl from isobutylene and / or tertiary butyl alcohol.
- a method for producing a catalyst for producing an acid is disclosed.
- Patent Documents 1 and 2 a production method by a rolling granulation method is disclosed as a method for producing a spherical shaped catalyst.
- a spherical carrier necessary for obtaining a desired catalyst particle size is put into a rolling granulator, and a liquid serving as a binder and a catalytically active component and / or precursor thereof are used as a carrier while rotating a molding machine.
- a spherical shaped catalyst is produced by sprinkling.
- Patent Document 3 and Patent Document 4 describe a method of oxidative dehydrogenation in the presence of a composite metal oxide catalyst mainly composed of molybdenum, bismuth, iron and cobalt.
- a composite metal oxide catalyst mainly composed of molybdenum, bismuth, iron and cobalt.
- Patent Document 5 describes a coated molded catalyst produced by mixing a pore-forming agent, and describes production on an industrial scale.
- Patent Document 5 does not clearly show the effect on the conversion rate of butene and the selectivity of butadiene by the production of the coating molded catalyst by mixing the pore forming agent. Further, in the method for producing a coated molded catalyst cited in Patent Document 5, the relative centrifugal acceleration is extremely low as compared with the method of this patent, which is a problem in terms of practical mechanical strength. It is an object of the present invention to provide a method for producing a shaped catalyst having sufficient mechanical strength and catalyst performance.
- the present inventors have demonstrated that a catalyst produced by giving a specific relative centrifugal acceleration by adjusting the diameter (rotation radius) and rotation speed of a rolling granulator in the production process of a molded catalyst has high catalyst performance.
- the present invention has been completed. That is, the present invention (1) Fixed bed oxidation reaction or fixed bed oxidation dehydration in which a catalyst powder containing a composite metal oxide containing molybdenum as an essential component is supported on an inert carrier by a rolling granulation method at a relative centrifugal acceleration of 1 to 35G.
- the method of manufacturing molded catalyst according to the composite metal oxide has a composition represented by the following formula (1) (1) Mo a Bi b Ni c Co d Fe f X g Y h O x formula (1)
- Mo, Bi, Ni, Co, Fe and O represent molybdenum, bismuth, nickel, cobalt, iron and oxygen, respectively
- X is tungsten, antimony, tin, zinc, chromium, manganese, magnesium
- Y represents at least one element selected from the group consisting of potassium, rubidium, calcium, barium, thallium and cesium
- b, c, d, f, g, h and x represent the number of atoms of molybdenum, bismuth, nickel, cobalt, iron, X, Y
- the produced molded catalyst is converted into n-butene by oxidative dehydrogenation.
- Unsaturated aldehyde and / or unsaturated which is oxidized to the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by gas phase catalytic oxidation reaction using the molded catalyst obtained by the production method described in (6)
- the present invention relates to a method for producing carboxylic acid.
- a molded catalyst having sufficient mechanical strength and catalyst performance can be produced.
- the composite metal oxide contained in the catalyst powder in the molded catalyst obtained in the present invention contains molybdenum as an essential element, other constituent elements and the constituent ratio thereof are not particularly limited, but preferably the following general formula (1 ) Mo a Bi b Ni c Co d Fe f X g Y h O x formula (1) (Wherein Mo, Bi, Ni, Co, Fe and O represent molybdenum, bismuth, nickel, cobalt, iron and oxygen, respectively, X is tungsten, antimony, tin, zinc, chromium, manganese, magnesium, silicon, aluminum Represents at least one element selected from the group consisting of cerium, tellurium, boron, germanium, zirconium and titanium, and Y represents at least one element selected from the group consisting of potassium, rubidium, calcium, barium, thallium and cesium , A, b, c, d, f, g, h and x represent the number of atoms of molybden
- the powder containing the catalytically active component is prepared by a known method such as a coprecipitation method or a spray drying method.
- nitrates, ammonium salts, hydroxides, oxides, acetates, and the like of various metal elements such as molybdenum, bismuth, nickel, cobalt, iron, X, and Y can be used, and are not particularly limited.
- Liquids or slurries containing different types of catalytically active components can be prepared by changing the type and / or amount of metal salt supplied to water, and powder containing the catalytically active components can be obtained by spray drying or the like.
- the powder thus obtained can be calcined at 200 to 600 ° C., preferably 300 to 500 ° C., preferably in air or a nitrogen stream, to obtain a catalytically active component (hereinafter referred to as pre-calcined powder).
- the pre-fired powder thus obtained can be used as a catalyst as it is, but in the present invention, it is molded in consideration of production efficiency and workability.
- the shape of the molded product is not particularly limited as long as the catalyst component can be coated, but it is preferably spherical from the viewpoint of production and actual use.
- pre-baked powders of differently prepared granules with different component compositions may be mixed and molded in any proportion.
- a method may be employed in which the operation of supporting different kinds of pre-fired powder on an inert carrier is repeated to form the pre-fired powder into a multilayer.
- a molding aid such as crystalline cellulose and / or a strength improver such as a ceramic whisker.
- the amount of the molding aid and / or strength improver used is preferably 30% by weight or less with respect to the pre-fired powder.
- the molding aid and / or the strength improver may be mixed in advance with the above pre-fired powder before molding, or may be added at the same time as or before or after the pre-fired powder is added to the molding machine. That is, if the molded catalyst finally used in the reaction is within the range of desired catalyst physical properties and / or catalyst composition, the above-mentioned molded product shape and molding method can be employed.
- a method in which the catalyst powder is coated and molded on the support by adding a pre-baked powder and, if necessary, a molding aid and a strength improver is preferable.
- binders that can be used include water, ethanol, methanol, propanol, polyhydric alcohol, polymer binder polyvinyl alcohol, silica sol aqueous solution of inorganic binder, etc.
- ethanol, methanol, propanol, polyhydric alcohol Alcohols are preferred, diols such as ethylene glycol and triols such as glycerin are more preferred, and aqueous solutions having a glycerin concentration of 5% by weight or more are particularly preferred.
- the amount of these binders used is usually 2 to 60 parts by weight based on 100 parts by weight of the pre-fired powder, but 10 to 50 parts by weight is preferable in the case of an aqueous glycerin solution.
- the binder may be added to the tumbling granulator at the same time as the pre-fired powder, or may be added alternately with the pre-fired powder.
- the size of the inert carrier is usually about 2 to 20 mm, on which the pre-fired powder is supported.
- the loading ratio is determined in consideration of the catalyst use conditions such as space velocity and feed hydrocarbon concentration. Usually, it is preferably supported so as to be 10 to 80% by weight.
- the relative centrifugal acceleration applied when rolling granulation is usually 1G to 35G, preferably 1.2G to 30G, more preferably 1.5G to 20G.
- the relative centrifugal acceleration is a numerical value representing the magnitude of the centrifugal force per unit weight when the carrier is put in a rolling granulator and rotated by the device, as a ratio with the gravitational acceleration. Is represented by the following formula (3). This increases in proportion to the absolute value of the distance from the center of rotation of the device and the square of the rotational speed.
- RCF 1118 ⁇ r ⁇ N 2 ⁇ 10 ⁇ 8 formula (3)
- RCF represents a relative centrifugal acceleration (G)
- r represents a distance (cm) from the center of rotation
- N represents a rotation speed (rpm).
- G relative centrifugal acceleration
- rpm rotation speed
- the relative centrifugal acceleration can be adjusted by increasing the rotational speed.
- the radius of rotation is not particularly limited, in practice, it is easy to use a commercially available device, and it is usually preferably about 0.1 to 2 m.
- the rotational speed is determined so as to be in the relative centrifugal acceleration range according to the formula (3) according to the size of the molding machine to be used.
- the input amount of the inert carrier to the molding machine is appropriately set according to the size of the molding machine, a desired production rate, etc., but it is preferably carried out in the range of 0.1 to 100 kg.
- Patent Document 5 also suggests that a coated molded catalyst containing molybdenum is produced by a rolling granulation method. However, the rotational speed at the time of rolling granulation is extremely slow compared with the method of the present invention. Therefore, the relative centrifugal acceleration is extremely low as compared with the method of the present invention.
- the molded catalyst that has undergone the tumbling granulation process can be charged into the reactor as it is, but in order to avoid high temperatures due to the burning of binders remaining in the catalyst during heating, and to ensure operational safety and health From the standpoint of securing practical strength, it is preferable to calcine again before using the molded catalyst that has undergone the rolling granulation step for the reaction.
- the firing temperature at the time of firing again is 450 to 650 ° C., the firing time is 3 to 30 hours, preferably 4 to 15 hours, and is appropriately set according to the reaction conditions to be used.
- the firing atmosphere may be either an air atmosphere or a nitrogen atmosphere, but industrially an air atmosphere is preferred.
- the catalyst of the present invention thus obtained has high mechanical strength.
- the friability is preferably 3% by weight or less, more preferably 1.5% by weight or less, and still more preferably 0.5% by weight or less.
- the catalyst of the present invention thus obtained is a step of producing acrolein and acrylic acid by vapor-phase catalytic oxidation of propylene with molecular oxygen or a molecular oxygen-containing gas, or a solid acid catalyst such as isobutylene or the catalyst of the present invention.
- a step of producing methacrolein and methacrylic acid by vapor-phase catalytic oxidation of tertiary butyl alcohol, which is known to easily convert to isobutylene and water, with molecular oxygen or a molecular oxygen-containing gas, or n-butene Can be used in a process for producing butadiene by gas phase catalytic oxidative dehydrogenation reaction with molecular oxygen or a molecular oxygen-containing gas.
- the flow method of the raw material gas may be a normal single-flow method or a recycling method, and can be carried out under generally used conditions and is not particularly limited.
- propylene as a starting material is 1 to 10% by volume at room temperature, preferably 4 to 9% by volume, molecular oxygen is 3 to 20% by volume, preferably 4 to 18% by volume, water vapor is 0 to 60% by volume, Preferably, 4 to 50% by volume, and a gas mixture of 20 to 80% by volume, preferably 30 to 60% by volume of an inert gas such as carbon dioxide and nitrogen, is charged on the catalyst of the present invention to 250 to 250%.
- the reaction can be carried out at 450 ° C. under normal pressure to 10 atm and a space velocity of 300 to 5000 h ⁇ 1 .
- n-butene as a starting material is 1 to 16% by volume, preferably 3 to 12% by volume, and molecular oxygen is 1 to 20% by volume, preferably 5% at room temperature.
- the reaction can be carried out by introducing the catalyst of the present invention filled in a tube at a space velocity of 300 to 5000 h ⁇ 1 at 250 to 450 ° C. and a pressure of normal pressure to 10 atm.
- the target compound in the case of an oxidation reaction in which the raw material compound is propylene, the target compound is (acrolein + acrylic acid).
- the target compound in the oxidation reaction in which the raw material compound is isobutylene and / or tertiary butyl alcohol is (methacrolein + methacrylic acid).
- the target compound in the case of an oxidative dehydrogenation reaction using n-butene as the starting compound, the target compound is butadiene.
- Example 1 Manufacture of catalyst While heating and stirring 3000 parts by weight of distilled water, 423.8 parts by weight of ammonium molybdate tetrahydrate and 3.0 parts by weight of potassium nitrate were dissolved to obtain an aqueous solution (A1). Separately, 302.7 parts by weight of cobalt nitrate hexahydrate, 162.9 parts by weight of nickel nitrate hexahydrate, and 145.4 parts by weight of ferric nitrate nonahydrate were dissolved in 1000 parts by weight of distilled water to prepare an aqueous solution.
- Aqueous solution (C1) was prepared by dissolving 164.9 parts by weight of bismuth nitrate pentahydrate in 200 parts by weight of distilled water acidified by adding (B1) and 42 parts by weight of concentrated nitric acid. (B1) and (C1) are mixed with the above aqueous solution (A1) successively with vigorous stirring, and the resulting suspension is dried using a spray drier and calcined at 440 ° C. for 6 hours to obtain a pre-calcined powder (D1) Got.
- the powder obtained by mixing 100 parts by weight of the pre-fired powder with 5 parts by weight of crystalline cellulose is defined by the above formula (2) as an inert carrier (spherical substance having a diameter of 4.5 mm mainly composed of alumina and silica).
- the weight of the carrier used for molding and the weight of the pre-fired powder were adjusted so that the loading ratio accounted for 50% by weight.
- a 20 wt% aqueous glycerin solution was used as a binder and supported and molded into a spherical shape with a diameter of 5.2 mm to obtain a molded catalyst (E1).
- a cylindrical molding machine having a diameter of 23 cm was used for support molding, and the number of rotations of the bottom plate was 150 rpm. The relative centrifugal acceleration at this time was 2.9G.
- the molded catalyst (F1) was obtained by calcining the molded catalyst (E1) at an calcination temperature of 510 ° C. for 4 hours in an air atmosphere.
- Example 2 A molded catalyst (F2) was produced in the same manner as in Example 1 except that the number of rotations of the bottom plate during molding was 210 rpm and the relative centrifugal acceleration was 5.7 G. Table 1 shows the oxidation reaction test results and strength measurement results of the molded catalyst F2.
- Example 3 A molded catalyst (F3) was produced in the same manner as in Example 1 except that the number of rotations of the bottom plate during molding was 260 rpm and the relative centrifugal acceleration was 8.7 G. Table 1 shows the oxidation reaction test results and strength measurement results of the molded catalyst (F3).
- Example 4 A molded catalyst (F4) was produced in the same manner as in Example 1 except that the number of rotations of the bottom plate during molding was 430 rpm and the relative centrifugal acceleration was 24 G. Table 1 shows the oxidation reaction test results and strength measurement results of the molded catalyst (F4).
- Comparative Example 1 A molded catalyst (V1) was produced in the same manner as in Example 1 except that the number of revolutions of the bottom plate during molding was 75 rpm and the relative centrifugal acceleration was 0.72 G. Table 1 shows the oxidation reaction test results and strength measurement results of the molded catalyst (V1).
- Example 5 Manufacture of catalyst While heating and stirring 12,000 parts by weight of distilled water, 3000 parts by weight of ammonium molybdate tetrahydrate and 55.2 parts by weight of cesium nitrate were dissolved to obtain an aqueous solution (A2). Separately, 2782 parts by weight of cobalt nitrate hexahydrate, 1144 parts by weight of ferric nitrate nonahydrate, and 412 parts by weight of nickel nitrate hexahydrate were dissolved in 2300 parts by weight of distilled water to prepare an aqueous solution (B2).
- An aqueous solution (C2) was prepared by dissolving 1167 parts by weight of bismuth nitrate pentahydrate in 1215 parts by weight of distilled water made acidic by adding 397 parts by weight of concentrated nitric acid.
- B2) and (C2) were sequentially mixed with the aqueous solution (A2) while vigorously stirring the aqueous solution (A2), the resulting suspension was dried using a spray dryer, and the resulting powder was 460 ° C.
- the powder obtained by mixing 100 parts by weight of the pre-fired powder with 5 parts by weight of crystalline cellulose is defined by the above formula (2) as an inert carrier (spherical substance having a diameter of 4.5 mm mainly composed of alumina and silica).
- the weight of the carrier used for molding and the weight of the pre-fired powder were adjusted so that the loading ratio accounted for 50% by weight.
- a molded catalyst (E5) was obtained by being supported and molded into a spherical shape having a diameter of 5.2 mm.
- a cylindrical molding machine having a diameter of 23 cm was used for support molding, and the number of rotations of the bottom plate was 260 rpm.
- the relative centrifugal acceleration at this time was 8.7G.
- the molded catalyst (E5) was calcined in an air atmosphere at a calcining temperature of 500 ° C. for 4 hours to obtain a molded catalyst (F5).
- Example 6 A molded catalyst (F6) was produced in the same manner as in Example 5 except that the number of rotations of the bottom plate during molding was 430 rpm and the relative centrifugal acceleration was 23.8 G. Table 1 shows the oxidation reaction test results and strength measurement results of the molded catalyst (F6).
- Example 7 Manufacture of catalyst
- a molded catalyst (F7) was produced with a rotational speed of the bottom plate at the time of molding of 260 rpm and a relative centrifugal acceleration of 8.7 G.
- Table 1 shows the results of the oxidative dehydrogenation reaction test and strength measurement of the molded catalyst (F7) carried out by the method described below.
- a gas in which the supply amounts of 1-butene, air, water, and nitrogen are set so that the raw material molar ratio is 1-butene: oxygen: nitrogen: water 1: 2.1: 10.4: 2.5
- the catalyst was introduced into the oxidation reactor at a space velocity of 1440 h ⁇ 1 , the reactor outlet pressure was set to 0 kPaG, and the catalyst performance was evaluated 15 hours after the start of the reaction.
- Example 8 A molded catalyst (F8) was produced in the same manner as in Example 7, except that the number of rotations of the bottom plate during molding was 430 rpm and the relative centrifugal acceleration was 23.8 G. Table 1 shows the results of the oxidative dehydrogenation reaction test and the strength measurement performed in the same manner as in Example 7 using the molded catalyst (F8).
- Comparative Example 2 A molded catalyst (V2) was produced in the same manner as in Example 7, except that the number of rotations of the bottom plate during molding was 550 rpm and the relative centrifugal acceleration was 38.9 G. Table 1 shows the results of the oxidative dehydrogenation reaction test and the strength measurement performed in the same manner as in Example 7 using the molded catalyst (V2).
- Comparative Example 3 A molded catalyst (V3) was produced in the same manner as in Example 7, except that the number of rotations of the bottom plate during molding was 60 rpm and the relative centrifugal acceleration was 0.46 G. Table 1 shows the results of the oxidative dehydrogenation reaction test and the strength measurement performed in the same manner as in Example 7 using the molded catalyst (V3).
- the shaped catalyst produced by the method of the present invention is a catalyst for producing acrolein and / or acrylic acid from propylene, methacrolein and / or methacrylic acid from isobutylene and / or tertiary butyl alcohol, or butadiene from n-butene. Useful as.
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Abstract
Description
一方、合成ゴムなどの原料として使用される重要な化学品原料であるブタジエンは、近年、世界的な自動車需要の高まりと環境意識向上により、省エネルギータイプの自動車タイヤの原料としての需要が急増している。しかし、C4留分の生産量が低下しているため、ブタジエン生産量の不足が続いており、今後さらにブタジエン供給量の不足が加速するものと予想されている。このため、新たなブタジエン製造方法の工業化が強く望まれている。
固定床反応装置で使用される触媒の形状は、その用途に応じ選択されるものであるが、リング形状、シリンダー形状、タブレット形状、ハニカム形状、三つ葉型、四葉型、さらには球状の触媒形状がよく使用されている。中でも球状の触媒は触媒を反応管に充填する作業、使用後の触媒を反応管から抜き出す作業の容易性から広く使用されている。
また、不活性担体に触媒活性成分を担持成型する方法は、発熱を伴う反応では逐次反応による目的生成物の選択性の低下をおさえ、触媒層の蓄熱を低減する目的等により、工業的に広く使用されている。特に有機化合物の酸化反応や酸化脱水素反応により目的生成物を選択的に製造する場合には、有効な方法として用いられている。
特許文献1及び2において、球状の成型触媒を製造する方法として転動造粒法による製造方法が開示されている。具体的には、所望の触媒粒径とするために必要な球状担体を転動造粒装置に入れ、成型機を回転させながらバインダーとなる液体と触媒活性成分および/またはその前駆体を担体にふりかけてゆくことで球状成型触媒が製造されている。
また、特許文献5には、細孔形成剤を混在させて製造する被覆成型触媒についての記載があり、工業スケールでの製造についても記載されている。
本発明は、十分な機械的強度と触媒性能をかねそなえた成型触媒を製造する方法を提供することにある。
すなわち本発明は、
(1)モリブデンを必須成分とする複合金属酸化物を含有する触媒粉末を、相対遠心加速度1~35Gにて転動造粒法により不活性担体に担持する、固定床酸化反応または固定床酸化脱水素反応用成型触媒の製造方法
(2)前記複合金属酸化物が下記式(1)で表される組成を有する上記(1)に記載の成型触媒の製造方法
MoaBibNicCodFefXgYhOx 式(1)
(式(1)中、Mo、Bi、Ni、Co、Fe及びOはそれぞれモリブデン、ビスマス、ニッケル、コバルト、鉄及び酸素を表し、Xはタングステン、アンチモン、錫、亜鉛、クロム、マンガン、マグネシウム、ケイ素、アルミニウム、セリウム、テルル、ホウ素、ゲルマニウム、ジルコニウムおよびチタンからなる群より選ばれる少なくとも一種の元素を表し、Yはカリウム、ルビジウム、カルシウム、バリウム、タリウムおよびセシウムからなる群より選ばれる少なくとも一種の元素を表し、a、b、c、d、f、g、h及びxは、それぞれモリブデン、ビスマス、ニッケル、コバルト、鉄、X、Yおよび酸素の原子数を表し、a=12、b=0.1~7、c+d=0.5~20、f=0.5~8、g=0~2、h=0.005~2であり、x=各元素の酸化状態によって決まる値である。)
(3)得られる成型触媒の磨損度が3重量%以下である(1)または(2)に記載の成型触媒の製造方法
(4)製造される成型触媒が、酸化脱水素反応によりn-ブテンよりブタジエンを製造する反応に用いる触媒である上記(1)~(3)のいずれか1項に記載の成型触媒の製造方法
(5)n-ブテンを、分子状酸素存在下、上記(4)に記載の製造方法により得られた成型触媒を用いて、気相接触酸化脱水素反応によりブタジエンに酸化脱水素する、ブタジエンの製造方法
(6)製造される成型触媒が、酸化反応により不飽和炭化水素より不飽和アルデヒドおよび/または不飽和カルボン酸を製造する反応に用いる触媒である上記(1)~(3)のいずれか1項に記載の成型触媒の製造方法
(7)不飽和炭化水素を、分子状酸素存在下、上記(6)に記載の製造方法により得られた成型触媒を用いて、気相接触酸化反応により、対応する不飽和アルデヒドおよび/または不飽和カルボン酸に酸化する、不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法
に関する。
なお、以下において本発明の製造方法により得られる成型触媒の好ましい用途である、プロピレンからアクロレインおよび/またはアクリル酸、イソブチレンおよび/またはターシャリーブチルアルコールからメタクロレインおよび/またはメタクリル酸、あるいはn-ブテンからブタジエンを製造するためのモリブデン-ビスマスを主要活性成分とする触媒を例に記載する。
MoaBibNicCodFefXgYhOx 式(1)
(式中、Mo、Bi、Ni、Co、Fe及びOはそれぞれモリブデン、ビスマス、ニッケル、コバルト、鉄及び酸素を表し、Xはタングステン、アンチモン、錫、亜鉛、クロム、マンガン、マグネシウム、ケイ素、アルミニウム、セリウム、テルル、ホウ素、ゲルマニウム、ジルコニウムおよびチタンからなる群より選ばれる少なくとも一種の元素を表し、Yはカリウム、ルビジウム、カルシウム、バリウム、タリウムおよびセシウムからなる群より選ばれる少なくとも一種の元素を表し、a、b、c、d、f、g、hおよびxは、それぞれモリブデン、ビスマス、ニッケル、コバルト、鉄、X、Yおよび酸素の原子数を表し、a=12、b=0.1~7、好ましくはb=0.5~4、c+d=0.5~20、好ましくはc+d=1~12、f=0.5~8、好ましくはf=0.5~5、g=0~2、好ましくはg=0~1、h=0.005~2、好ましくはh=0.01~0.5であり、x=各元素の酸化状態によって決まる値である。)で表記することが出来る。
こうして得られた粉末を200~600℃、好ましくは300~500℃で、好ましくは空気または窒素気流中にて焼成し触媒活性成分(以下、予備焼成粉末という)を得ることができる。
使用できるバインダーの具体例としては、水やエタノール、メタノール、プロパノール、多価アルコール、高分子系バインダーのポリビニールアルコール、無機系バインダーのシリカゾル水溶液等が挙げられるが、エタノール、メタノール、プロパノール、多価アルコールが好ましく、エチレングリコール等のジオールやグリセリン等のトリオール等がより好ましく、特にグリセリンの濃度が5重量%以上の水溶液が好ましい。グリセリン水溶液を適量使用することにより成型性が良好となり、機械的強度の高い、高活性かつ高性能な触媒が得られる。これらバインダーの使用量は、予備焼成粉末100重量部に対して通常2~60重量部であるが、グリセリン水溶液の場合は10~50重量部が好ましい。担持に際してバインダーは転動造粒機に予備焼成粉末と同時に添加しても、予備焼成粉末と交互に添加してもよい。
通常は、10~80重量%となるように担持させるのが好ましい。成型後の触媒の担持率は以下の式(2)で定義される
担持率(%)=(予備焼成粉末の重量/(予備焼成粉末の重量+担体の重量))×100 式(2)
RCF=1118×r×N2×10-8 式(3)
式(3)において、RCFは相対遠心加速度(G)、rは回転中心からの距離(cm)、Nは回転速度(rpm)を表す。
成型には、一般的な大きさの装置を使用することができる。
回転半径の小さな成型機を使用する場合は、回転数を上げることで相対遠心加速度を調節することが出来る。回転半径は特に制限されないが、実際には市販されている機器を使用することが簡便であり、通常は0.1~2m程度とすることが好ましい。回転速度は、使用する成型機の大きさにより、上記式(3)に従って、上記の相対遠心加速度範囲になるように決定される。成型機への不活性担体の投入量は、成型機の大きさ、所望の生産速度等から適宜設定されるものであるが、0.1~100kgの範囲で実施することが好ましい。
なお、特許文献5にも、モリブデンを含有する被覆成型触媒を転動造粒法により製造することが示唆されている。しかし、その転動造粒時の回転速度は本発明の方法に比べて極端に遅い。そのため、相対遠心加速度も本発明の方法に比べて極めて低いものである。
n-ブテンの酸化脱水素反応の場合、例えば出発原料物質としてのn-ブテンが常温で1~16容量%、好ましくは3~12容量%、分子状酸素が1~20容量%、好ましくは5~16容量%、水蒸気が0~60容量%、好ましくは4~50容量%、二酸化炭素、窒素等の不活性ガスが64~98容量%、好ましくは72~92容量%からなる混合ガスを反応管中に充填した本発明の触媒上に250~450℃で、常圧~10気圧の圧力下で、空間速度300~5000h-1で導入し反応を行うことができる。
なお、本発明における転化率および収率はそれぞれ次の通り定義される。
収率(モル%)=(生成した目的化合物のモル数/供給した原料化合物のモル数)×100
(触媒の製造)
蒸留水3000重量部を加熱攪拌しながらモリブデン酸アンモニウム四水和物423.8重量部と硝酸カリウム3.0重量部を溶解して水溶液(A1)を得た。別に、硝酸コバルト六水和物302.7重量部、硝酸ニッケル六水和物162.9重量部、硝酸第二鉄九水和物145.4重量部を蒸留水1000重量部に溶解して水溶液(B1)を、また濃硝酸42重量部を加えて酸性にした蒸留水200重量部に硝酸ビスマス五水和物164.9重量部を溶解して水溶液(C1)をそれぞれ調製した。上記水溶液(A1)に(B1)、(C1)を順次、激しく攪拌しながら混合し、生成した懸濁液をスプレードライヤーを用いて乾燥し440℃で6時間焼成して予備焼成粉末(D1)を得た。このときの触媒活性成分の酸素を除いた組成比は原子比でMo=12、Bi=1.7、Ni=2.8、Fe=1.8、Co=5.2、K=0.15であった。
その後、予備焼成粉末100重量部に結晶セルロース5重量部を混合した粉末を不活性担体(アルミナ、シリカを主成分とする直径4.5mmの球状物質)に、上記式(2)で定義される担持率が、50重量%を占める割合になるように、成型に使用する担体重量および予備焼成粉末重量を調整した。20重量%グリセリン水溶液をバインダーとして使用し、直径5.2mmの球状に担持成型して成型触媒(E1)を得た。
担持成型には直径23cmの円柱状の成型機を使用し、底板の回転数を150rpmとした。このときの相対遠心加速度は2.9Gであった。
成型触媒(E1)を、焼成温度510℃で4時間、空気雰囲気下で焼成することで成型触媒(F1)を得た。
熱媒体としてアルミナ粉末を空気により流動させるためのジャケット及び触媒層温度を測定するための熱電対を管軸に設置した、内径28.4mmのステンレス製反応器に成型触媒(F1)を68ml充填し、反応浴温度を320℃にした。ここに原料モル比がプロピレン:酸素:窒素:水=1:1.7:6.4:3.0となるようにプロピレン、空気、水の供給量を設定したガスを空間速度862h-1で酸化反応器内へ導入し、反応器出口圧力を0kPaGとして反応開始後20時間後に触媒性能を評価した。結果を表1に示した。
成型触媒(F1) 50.0gを、内部に一枚の邪魔板を備えた、半径14cmの円筒型回転機に仕込み23rpmで10分間回転させた。その後剥離した粉末を1.7mm間隔のふるいで除去し、残存量(g)を測定し、以下の式から磨損度を求めた。結果を表1に示した。
磨損度(%)=(50.0-残存量)/50.0 × 100
成型の際の底板の回転数を210rpmとして、相対遠心加速度を5.7Gとしたこと以外は実施例1と同様の方法で成型触媒(F2)を製造した。成型触媒F2の酸化反応試験結果と強度測定結果を表1に示した。
成型の際の底板の回転数を260rpmとして、相対遠心加速度を8.7Gとしたこと以外は実施例1と同様の方法で成型触媒(F3)を製造した。成型触媒(F3)の酸化反応試験結果と強度測定結果を表1に示した。
成型の際の底板の回転数を430rpmとして、相対遠心加速度を24Gとしたこと以外は実施例1と同様の方法で成型触媒(F4)を製造した。成型触媒(F4)の酸化反応試験結果と強度測定結果を表1に示した。
成型の際の底板の回転数を75rpmとして、相対遠心加速度を0.72Gとしたこと以外は実施例1と同様の方法で成型触媒(V1)を製造した。成型触媒(V1)の酸化反応試験結果と強度測定結果を表1に示した。
(触媒の製造)
蒸留水12000重量部を加熱攪拌しながらモリブデン酸アンモニウム四水和物3000重量部と硝酸セシウム55.2重量部を溶解して水溶液(A2)を得た。別に、硝酸コバルト六水和物2782重量部、硝酸第二鉄九水和物1144重量部、硝酸ニッケル六水和物412重量部を蒸留水2300重量部に溶解して水溶液(B2)を、また濃硝酸397重量部を加えて酸性にした蒸留水1215重量部に硝酸ビスマス五水和物1167重量部を溶解して水溶液(C2)をそれぞれ調製した。上記水溶液(A2)に(B2)、(C2)を順次、水溶液(A2)を激しく攪拌しながら混合し、生成した懸濁液を、スプレードライヤーを用いて乾燥し、得られた粉末を460℃で5時間焼成して予備焼成粉末(D2)を得た。このときの触媒活性成分の酸素を除いた組成比は原子比でMo=12、Bi=1.7、Fe=2.0、Co=6.75、Ni=1.0、Cs=0.20であった。
その後、予備焼成粉末100重量部に結晶セルロース5重量部を混合した粉末を不活性担体(アルミナ、シリカを主成分とする直径4.5mmの球状物質)に、上記式(2)で定義される担持率が、50重量%を占める割合になるように、成型に使用する担体重量および予備焼成粉末重量を調整した。20重量%グリセリン水溶液をバインダーとして使用し、直径5.2mmの球状に担持成型して成型触媒(E5)を得た。
担持成型には直径23cmの円柱状の成型機を使用し、底板の回転数を260rpmとした。このときの相対遠心加速度は8.7Gであった。
成型触媒(E5)を、焼成温度500℃で4時間、空気雰囲気下で焼成することで成型触媒(F5)を得た。
熱媒体としてアルミナ粉末を空気により流動させるためのジャケット及び触媒層温度を測定するための熱電対を管軸に設置した、内径22mmのステンレス製反応器に成型触媒(F5)を34ml充填し、反応浴温度を350℃にした。ここに原料モル比がイソブチレン:酸素:窒素:水=1:2.2:12.5:1.0となるようにイソブチレン、空気、水、窒素の供給量を設定したガスを空間速度1200h-1で酸化反応器内へ導入し、反応器出口圧力を0.5kPaGとして反応開始後20時間後に触媒性能を評価した。結果を表1に示した。
実施例1と同一の方法で磨損度を求めた。結果を表1に示した。
成型の際の底板の回転数を430rpmとして、相対遠心加速度を23.8Gとしたこと以外は実施例5と同様の方法で成型触媒(F6)を製造した。成型触媒(F6)の酸化反応試験結果と強度測定結果を表1に示した。
(触媒の製造)
実施例5と同様の方法で、成型の際の底板の回転数を260rpmとし、相対遠心加速度を8.7Gとして成型触媒(F7)を製造した。以下に記載する方法で行った成型触媒(F7)の酸化脱水素反応試験結果と強度測定結果を表1に示した。
熱媒体としてアルミナ粉末を空気により流動させるためのジャケット及び触媒層温度を測定するための熱電対を管軸に設置した、内径28.4mmのステンレス製反応器に成型触媒(F7)を53ml充填し、反応浴温度を340℃にした。ここに原料モル比が1-ブテン:酸素:窒素:水=1:2.1:10.4:2.5となるように1-ブテン、空気、水、窒素の供給量を設定したガスを空間速度1440h-1で酸化反応器内へ導入し、反応器出口圧力を0kPaGとして反応開始後15時間後に触媒性能を評価した。
成型の際の底板の回転数を430rpmとして、相対遠心加速度を23.8Gとしたこと以外は実施例7と同様の方法で成型触媒(F8)を製造した。成型触媒(F8)を用いて実施例7と同様にして行った酸化脱水素反応試験結果と強度測定結果を表1に示した。
成型の際の底板の回転数を550rpmとして、相対遠心加速度を38.9Gとしたこと以外は実施例7と同様の方法で成型触媒(V2)を製造した。成型触媒(V2)を用いて実施例7と同様にして行った酸化脱水素反応試験結果と強度測定結果を表1に示した。
成型の際の底板の回転数を60rpmとして、相対遠心加速度を0.46Gとしたこと以外は実施例7と同様の方法で成型触媒(V3)を製造した。成型触媒(V3)を用いて実施例7と同様にして行った酸化脱水素反応試験結果と強度測定結果を表1に示した。
また、成型触媒(F5)あるいは成型触媒(F6)を用いて、イソブチレンの酸化反応を行った結果、良好な原料転化率、および有効収率が得られた。
同様に、成型触媒(F7)あるいは成型触媒(F8)用いて、1-ブテンの酸化脱水素反応を行った結果、良好な原料転化率、および有効収率が得られたが、本発明の範囲以上の相対遠心加速度の条件で成型した成型触媒(V2)では、同条件で実施した1-ブテンの酸化脱水素反応において、原料転化率が明らかに低下していることがわかる。
以上の結果から、本発明の方法によれば、触媒強度に優れ、良好な反応成績を示す触媒が製造できることは明らかである。
なお、本出願は、2012年4月23日付で出願された日本国特許出願(特願2012-098259)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。
本発明の方法により製造された成型触媒は、プロピレンからアクロレインおよび/またはアクリル酸、イソブチレンおよび/またはターシャリーブチルアルコールからメタクロレインおよび/またはメタクリル酸、あるいはn-ブテンからブタジエンを製造するための触媒として有用である。
Claims (7)
- モリブデンを必須成分とする複合金属酸化物を含有する触媒粉末を、相対遠心加速度1~35Gにて転動造粒法により不活性担体に担持する、固定床酸化反応または固定床酸化脱水素反応用成型触媒の製造方法。
- 前記複合金属酸化物が下記式(1)で表される組成を有する請求項1に記載の成型触媒の製造方法。
MoaBibNicCodFefXgYhOx 式(1)
(式(1)中、Mo、Bi、Ni、Co、Fe及びOはそれぞれモリブデン、ビスマス、ニッケル、コバルト、鉄及び酸素を表し、Xはタングステン、アンチモン、錫、亜鉛、クロム、マンガン、マグネシウム、ケイ素、アルミニウム、セリウム、テルル、ホウ素、ゲルマニウム、ジルコニウムおよびチタンからなる群より選ばれる少なくとも一種の元素を表し、Yはカリウム、ルビジウム、カルシウム、バリウム、タリウムおよびセシウムからなる群より選ばれる少なくとも一種の元素を表し、a、b、c、d、f、g、h及びxは、それぞれモリブデン、ビスマス、ニッケル、コバルト、鉄、X、Yおよび酸素の原子数を表し、a=12、b=0.1~7、c+d=0.5~20、f=0.5~8、g=0~2、h=0.005~2であり、x=各元素の酸化状態によって決まる値である。) - 得られる成型触媒の磨損度が3重量%以下である請求項1または2に記載の成型触媒の製造方法。
- 製造される成型触媒が、酸化脱水素反応によりn-ブテンよりブタジエンを製造する反応に用いる触媒である請求項1~3のいずれか1項に記載の成型触媒の製造方法。
- n-ブテンを、分子状酸素存在下、請求項4に記載の製造方法により得られた成型触媒を用いて、気相接触酸化脱水素反応によりブタジエンに酸化脱水素する、ブタジエンの製造方法。
- 製造される成型触媒が、酸化反応により不飽和炭化水素より不飽和アルデヒドおよび/または不飽和カルボン酸を製造する反応に用いる触媒である請求項1~3のいずれか1項に記載の成型触媒の製造方法。
- 不飽和炭化水素を、分子状酸素存在下、請求項6に記載の製造方法により得られた成型触媒を用いて、気相接触酸化反応により、対応する不飽和アルデヒドおよび/または不飽和カルボン酸に酸化する、不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法。
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WO2015053269A1 (ja) * | 2013-10-10 | 2015-04-16 | 日本化薬株式会社 | 不飽和カルボン酸の製造方法、及び担持触媒 |
US9751822B2 (en) | 2013-10-10 | 2017-09-05 | Nippon Kayaku Kabushiki Kaisha | Method for producing unsaturated carboxylic acid and supported catalyst |
KR20160127095A (ko) * | 2014-02-28 | 2016-11-02 | 바스프 에스이 | 안장형 지지체를 갖는 산화 촉매 |
KR102358652B1 (ko) * | 2014-02-28 | 2022-02-07 | 바스프 에스이 | 안장형 지지체를 갖는 산화 촉매 |
EP3059219A4 (en) * | 2014-12-16 | 2017-11-01 | LG Chem, Ltd. | Butadiene production method |
CN105916579A (zh) * | 2014-12-16 | 2016-08-31 | Lg化学株式会社 | 制备丁二烯的方法 |
JP2017502926A (ja) * | 2014-12-16 | 2017-01-26 | エルジー・ケム・リミテッド | ブタジエンの製造方法 |
US9751819B2 (en) | 2014-12-16 | 2017-09-05 | Lg Chem, Ltd. | Method of preparing butadiene |
WO2017047710A1 (ja) * | 2015-09-16 | 2017-03-23 | 日本化薬株式会社 | 共役ジオレフィン製造用触媒と、その製造方法 |
JPWO2017047710A1 (ja) * | 2015-09-16 | 2018-07-05 | 日本化薬株式会社 | 共役ジオレフィン製造用触媒と、その製造方法 |
JP2017124384A (ja) * | 2016-01-15 | 2017-07-20 | 三菱ケミカル株式会社 | 複合酸化物触媒の製造方法 |
JP2020535002A (ja) * | 2017-11-28 | 2020-12-03 | エルジー・ケム・リミテッド | ブテンの酸化的脱水素化反応用触媒およびその製造方法 |
US11648536B2 (en) | 2017-11-28 | 2023-05-16 | Lg Chem, Ltd. | Catalyst for oxidative dehydrogenation of butene and method for producing the same |
WO2020013064A1 (ja) * | 2018-07-09 | 2020-01-16 | 日本化薬株式会社 | 触媒及びそれを用いた化合物の製造方法 |
CN112399886A (zh) * | 2018-07-09 | 2021-02-23 | 日本化药株式会社 | 催化剂和使用了该催化剂的化合物的制造方法 |
JPWO2020013064A1 (ja) * | 2018-07-09 | 2021-08-05 | 日本化薬株式会社 | 触媒及びそれを用いた化合物の製造方法 |
JP7224351B2 (ja) | 2018-07-09 | 2023-02-17 | 日本化薬株式会社 | 触媒及びそれを用いた化合物の製造方法 |
JP2021000610A (ja) * | 2019-06-24 | 2021-01-07 | 日本化薬株式会社 | 触媒およびその製造方法 |
JP7191482B2 (ja) | 2019-06-24 | 2022-12-19 | 日本化薬株式会社 | 触媒およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
TW201406455A (zh) | 2014-02-16 |
EP2842626A1 (en) | 2015-03-04 |
TWI569872B (zh) | 2017-02-11 |
JPWO2013161702A1 (ja) | 2015-12-24 |
CN104245127A (zh) | 2014-12-24 |
EP2842626A4 (en) | 2015-10-28 |
KR101745555B1 (ko) | 2017-06-09 |
TWI574731B (zh) | 2017-03-21 |
JP5970542B2 (ja) | 2016-08-17 |
CN104245127B (zh) | 2016-03-30 |
JPWO2013161703A1 (ja) | 2015-12-24 |
KR20150008864A (ko) | 2015-01-23 |
US9573127B2 (en) | 2017-02-21 |
SA113340492B1 (ar) | 2016-03-03 |
TW201412396A (zh) | 2014-04-01 |
US20150126774A1 (en) | 2015-05-07 |
SG11201406832UA (en) | 2014-11-27 |
JP6034372B2 (ja) | 2016-11-30 |
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